JP2001172286A - Triamino- and fluoroalkyl-functional organosiloxane - Google Patents

Triamino- and fluoroalkyl-functional organosiloxane

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Publication number
JP2001172286A
JP2001172286A JP2000345062A JP2000345062A JP2001172286A JP 2001172286 A JP2001172286 A JP 2001172286A JP 2000345062 A JP2000345062 A JP 2000345062A JP 2000345062 A JP2000345062 A JP 2000345062A JP 2001172286 A JP2001172286 A JP 2001172286A
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JP
Japan
Prior art keywords
general formula
organosiloxane
composition
water
integer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2000345062A
Other languages
Japanese (ja)
Other versions
JP4938169B2 (en
Inventor
Peter Dr Jenkner
イェンクナー ペーター
Burkhard Dr Standke
シュタントケ ブルクハルト
Jaroslaw Monkiewicz
モンキーヴィッツ ヤラスロフ
Michael Dr Horn
ホルン ミヒャエル
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Degussa Huels AG
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Filing date
Publication date
Priority claimed from DE1999155047 external-priority patent/DE19955047C2/en
Application filed by Degussa GmbH, Degussa Huels AG filed Critical Degussa GmbH
Publication of JP2001172286A publication Critical patent/JP2001172286A/en
Application granted granted Critical
Publication of JP4938169B2 publication Critical patent/JP4938169B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
    • C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Abstract

PROBLEM TO BE SOLVED: To provide the subject organosiloxane having the maximal number of fluoroalkyl groups compared to the number of aminoalkyl groups. SOLUTION: This organosiloxane is such as to have at least one triamino group of formula I: [NHx(CH2)aNHy(CH2)bNHz]- [in this case, the group is bound, via at least one 1-4C N-bound alkylene group, to at least one silicon atom; (a) and b are each an integer of 1-6; x is 0, 1 or 2; y is 0 or 1; z is 0, 1 or 2; and (x+y+z)<=4] and at least one Si-C-bound fluoroalkyl group of formula II: F3C(CF2)r(CH2)s- [wherein, r is an integer of 0-18; and s is 0 or 2].

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、新規トリアミノ−
及びフルオルアルキル官能性オルガノシロキサンに関す
る。更に本発明は、その製造、相応するオルガノシロキ
サンを含有する組成物又は薬剤並びにその使用に関す
る。The present invention relates to a novel triamino-
And fluoroalkyl-functional organosiloxanes. The invention further relates to the preparation thereof, to the compositions or medicaments containing the corresponding organosiloxanes and to their use.

【０００２】特に本発明は、アミノアルキル−及びフル
オルアルキル官能性、ヒドロキシ基及び／又はアルコキ
シ基含有のオルガノシロキサン、水、場合によりアルコ
ールの含量及び場合により酸の含量を含有する組成物に
関する。本特許明細書では、水性組成物中に含有されて
いるヒドロキシ基−及び／又はアルコキシ基含有のオル
ガノシロキサンとは、化学的知識により完全に又は部分
的に加水分解されている、即ち、平衡状態の範囲でヒド
ロキシ−又はアルコキシ基を含有することができるよう
な化合物のことである。In particular, the present invention relates to compositions containing organosiloxanes containing aminoalkyl- and fluoroalkyl functionality, hydroxy and / or alkoxy groups, water, optionally alcohol and optionally acid. In this patent specification, the hydroxy- and / or alkoxy-containing organosiloxane contained in the aqueous composition is completely or partially hydrolyzed by chemical knowledge, ie And a compound capable of containing a hydroxy- or alkoxy group.

【０００３】[0003]

【従来の技術】フルオルアルキルアルコキシシラン又は
相応する重縮合物を製造すること及び疎水剤並びに疎油
剤として使用することは以前から公知である（例えばＤ
Ｅ−ＰＳ８３４００２、ＵＳ３０１３０６６、ＧＢ９３
５３８０、ＤＥ−ＯＳ３１００５５５、ＥＰ０３８２５
５７Ａ１、ＥＰ０４９３７４７Ｂ１、ＥＰ０５８７６６
７Ｂ１及びＤＥ−ＯＳ１９５４４７６３）。The preparation of fluoroalkylalkoxysilanes or the corresponding polycondensates and their use as hydrophobicizing and oleophobic agents has been known for some time (for example, D).
E-PS8344002, US3013066, GB93
5380, DE-OS3100555, EP03825
57A1, EP0493747B1, EP0587766
7B1 and DE-OS 19544763).

【０００４】フルオルアルキルアルコキシシランは、非
常に高価な製品であるために、通常は濃縮形で使用する
ことはない。更にフルオルアルキルアルコキシシランは
水に可溶性でない。[0004] Fluoroalkylalkoxysilanes are not usually used in concentrated form, since they are very expensive products. Furthermore, fluoroalkylalkoxysilanes are not soluble in water.

【０００５】フルオルアルキル官能性シラン並びに相応
する共縮合体の十分に安定な溶液又は製剤を得るため
に、有機溶剤又は乳化剤も使用されている（例えばＤＥ
−ＯＳ３４４７６３６、ＤＥ−ＰＳ３６１３３８４、Ｗ
Ｏ９５／２３８３０、ＷＯ９５／２３８０４、ＷＯ９６
／０６８９５、ＷＯ９７／２３４３２、ＥＰ０８４６７
１６Ａ１）。Organic solvents or emulsifiers have also been used to obtain sufficiently stable solutions or formulations of the fluoroalkyl-functional silanes and the corresponding cocondensates (eg DE)
-OS3447636, DE-PS3613384, W
O95 / 23830, WO95 / 23804, WO96
/ 06895, WO97 / 23432, EP08467
16A1).

【０００６】溶剤−並びに乳化剤含有製剤並びに高い割
合のアルコキシ基を有するオルガノシロキサンの欠点
は、このような系が生態学的及び作業上の安全技術的理
由から望ましくないことである。従って、できる限り僅
かな揮発性有機化合物（略称：“ＶＯＣ”＝“ｖｏｌａ
ｔｉｌｅ ｏｒｇａｎｉｃ ｃｏｍｐｏｕｎｄｓ”）割
合を有する水性系を提供することが益々求められてい
る。A disadvantage of solvent- and emulsifier-containing formulations and organosiloxanes with a high proportion of alkoxy groups is that such systems are undesirable for ecological and operational safety reasons. Therefore, as few volatile organic compounds as possible (abbreviation: “VOC” = “vola”)
There is an increasing need to provide aqueous systems having a Tile organic compounds ") ratio.

【０００７】窒素含有又はアミノアルキル−及びフルオ
ルアルキル官能性及び主としてアルコキシ基不含のオル
ガノシロキサンは、表面の撥水、撥油及び撥汚れ加工用
の乳化剤−又は界面活性剤不含の薬剤中の水溶性成分と
して公知である（ＤＥ−ＯＳ１５１８５５１、ＥＰ０７
３８７７１Ａ１、ＥＰ０８４６７１７Ａ１）。Nitrogen-containing or aminoalkyl- and fluoroalkyl-functional and predominantly alkoxy-free organosiloxanes are used in emulsifier-free or surfactant-free drugs for surface water, oil and soil repellency processing. Known as water-soluble components (DE-OS 1518551, EP07
38771A1, EP0846717A1).

【０００８】前記水性系では、良好な水溶性を確実なも
のとするために、常に比較的高いアミノアルキル基割合
を使用せねばならない。高いアミノアルキル基割合は他
方では逆効果である。それは、これが親水性を有し、従
ってできる限り疎水性の作用を有する系を提供する試み
とは相反することになるからである。In said aqueous systems, a relatively high proportion of aminoalkyl groups must always be used in order to ensure good water solubility. A high aminoalkyl content is, on the other hand, counterproductive. This is inconsistent with attempts to provide a system that is hydrophilic and therefore has as hydrophobic a function as possible.

【０００９】[0009]

【発明が解決しようとする課題】本発明の根底をなす課
題は、その他の水溶性のアミノアルキル−及びフルオル
アルキル官能性オルガノシロキサンを提供することであ
る。特に本発明の課題は、アミノアルキル基の数と比べ
てできる限り多い数のフルオルアルキル基を有するオル
ガノシロキサンを提供することであった。It is an object underlying the present invention to provide other water-soluble aminoalkyl- and fluoroalkyl-functional organosiloxanes. In particular, an object of the present invention was to provide an organosiloxane having as many fluoroalkyl groups as possible compared to the number of aminoalkyl groups.

【００１０】[0010]

【課題を解決するための手段】この課題は、本発明によ
り特許請求項の記載により解決することができる。This object can be achieved according to the invention by means of the claims.

【００１１】さて、意外にも、水溶性のトリアミノ−及
びフルオルアルキル官能性、ヒドロキシ基−及び／又は
アルコキシ基含有のオルガノシロキサン又は相応するオ
ルガノシロキサンの混合物、水、場合によりアルコール
の含量及び場合により酸の含量から成る、低粘性の、即
ち有利には＜１００ｍＰａｓの、通常透明から僅かに白
濁した、水と希釈する際でも有利に数ヶ月間貯蔵安定性
の組成物が、 ｉ）一般式ＩＩＩａ ＮＨ2（ＣＨ2）2ＮＨ（ＣＨ2）2ＮＨ（ＣＨ2）3Ｓｉ
（Ｒ’）j（ＯＲ）(3-j)（ＩＩＩａ） ［式中、Ｒ及びＲ’は同一又は異なるものであり、Ｃ原
子１〜４個を有する線状又は枝分れアルキル基を表わ
し、ｊは０又は１である］及び／又は 一般式ＩＩＩｂ ［ＮＨ2（ＣＨ2）2］2Ｎ（ＣＨ2）3Ｓｉ（Ｒ’）k（Ｏ
Ｒ）(3-k) （ＩＩＩｂ） ［式中、Ｒ及びＲ’は同一又は異なるものであり、Ｃ原
子１〜４個を有する線状又は枝分れアルキル基を表わ
し、ｋは０又は１である］のアミノアルキルアルコキシ
シラン少なくとも１種及び／又は 一般式ＩＩＩｃ ［ＮＨx（ＣＨ2）aＮＨy（ＣＨ2）bＮＨz］・［（Ｃ
Ｈ2）cＳｉ（Ｒ’）d（ＯＲ）(3-d)］e （ＩＩＩｃ） ［式中、Ｒ及びＲ’は同一又は異なるものであり、Ｃ原
子１〜４個を有する線状又は枝分れアルキル基を表わ
し、ａは１〜６の整数を表わし、ｂは１、２、３、４、
５又は６であり、ｃは１、２、３又は４であり、ｄは０
又は１であり、ｅは１、２、３、４又は５であり、ｘは
０又は１又は２であり、ｙは０又は１であり、ｚは０又
は１又は２でありかつ（ｘ＋ｙ＋ｚ）≦４の条件を有
し、その際、ｅは（ｘ＋ｙ＋ｚ）＝０の場合には数値５
であり、（ｘ＋ｙ＋ｚ）＝１の場合にはｅ＝４であり、
（ｘ＋ｙ＋ｚ）＝２の場合にはｅ＝３であり、（ｘ＋ｙ
＋ｚ）＝３の場合にはｅ＝２であり、（ｘ＋ｙ＋ｚ）＝
４の場合にはｅ＝１である］の“ビスプロダクト”又は
“ビスプロダクト”の混合物及び ｉｉ）一般式ＩＶ Ｆ3Ｃ（ＣＦ2）r（ＣＨ2）sＳｉ（Ｒ”）t（ＯＲ）
(3-t) （ＩＶ） ［式中、ｒは０〜１８の整数であり、ｓは０又は２であ
り、ｔは０又は１であり、Ｒ及びＲ”は同一又は異なる
ものであり、Ｃ原子１〜４個を有する線状又は枝分れア
ルキル基を表わす］のフルオルアルキルアルコキシラン
少なくとも１種を混合し、場合によりアルコール、水又
は水／アルコール混合物並びに場合により触媒を添加
し、反応させ又は成分を反応させ、即ち、場合により前
加水分解し、加水分解し、共縮合させ、アルコールを完
全にか又は部分的に、即ち有利には残量を５質量％より
少なくなるよう、除去し、場合により得られた生成物混
合物を無機又は有機酸の添加によりｐＨ＜１２に調整す
ることにより得られることを見出した。組成物がｐＨ値
＜１１を有するのが好適である。Surprisingly, it is surprising that the content of water-soluble triamino- and fluoroalkyl-functional, hydroxy- and / or alkoxy-containing organosiloxanes or mixtures of the corresponding organosiloxanes, water, optionally alcohol, and A low-viscosity, i.e. preferably <100 mPas, composition which is usually clear to slightly cloudy and which is stable for several months even when diluted with water, consisting of an acid content of: IIIa NH 2 (CH 2 ) 2 NH (CH 2 ) 2 NH (CH 2 ) 3 Si
(R ′) j (OR) (3-j) (IIIa) wherein R and R ′ are the same or different and represent a linear or branched alkyl group having 1 to 4 C atoms. , J is 0 or 1] and / or general formula IIIb [NH 2 (CH 2 ) 2 ] 2 N (CH 2 ) 3 Si (R ′) k (O
R) (3-k) (IIIb) wherein R and R ′ are the same or different and represent a linear or branched alkyl group having 1 to 4 C atoms, and k is 0 or 1 aminoalkyl alkoxysilanes at least one and / or the general formula IIIc of the is] [NH x (CH 2) a NH y (CH 2) b NH z] · [(C
H 2 ) c Si (R ′) d (OR) (3-d) ] e (IIIc) wherein R and R ′ are the same or different and are linear or having 1 to 4 C atoms or A represents an integer of 1 to 6, b represents 1, 2, 3, 4,
5 or 6, c is 1, 2, 3 or 4, and d is 0
Or 1, e is 1, 2, 3, 4 or 5, x is 0 or 1 or 2, y is 0 or 1, z is 0 or 1 or 2, and (x + y + z) ≦ 4, where e is the numerical value 5 if (x + y + z) = 0
And when (x + y + z) = 1, e = 4,
When (x + y + z) = 2, e = 3, and (x + y)
+ Z) = 3, e = 2, and (x + y + z) =
E = 1 in the case of 4) or a mixture of “bisproducts” and ii) the general formula IV F 3 C (CF 2 ) r (CH 2 ) s Si (R ″) t (OR )
(3-t) (IV) wherein r is an integer of 0 to 18, s is 0 or 2, t is 0 or 1, R and R ″ are the same or different, A linear or branched alkyl radical having 1 to 4 C atoms], and optionally adding an alcohol, water or a water / alcohol mixture and optionally a catalyst, Reacting or reacting the components, i.e. optionally pre-hydrolyzing, hydrolyzing and co-condensing, so that the alcohol is completely or partially, i.e. preferably with a residual amount of less than 5% by weight. It has been found that it can be obtained by adjusting the pH of the resulting product mixture to pH <12 by adding inorganic or organic acids, it is preferred that the composition has a pH value of <11.

【００１２】更に本発明による組成物は、相応して処理
された鉱物表面のなお改善された撥液体特性−親水性並
びに疎水性の標準試験液体を使用下で（ＤｕＰｏｎｔ社
の“ＴｅｆｌｏｎR ｓｐｅｃｉｆｉｃａｔｉｏｎ ｔ
ｅｓｔ ｋｉｔ”による試験）−を生じる。これに関し
ては実施例を参照にされたい。In addition, the compositions according to the invention can be prepared using the standard test liquids of the hydrophilic and hydrophobic properties which are still improved by the correspondingly treated mineral surfaces-hydrophilic and hydrophobic (Teflon® specification from DuPont).
est kit ").-see in the Examples.

【００１３】特に、１：≦３．５、有利には１：３〜
１：０．５、特に有利には１：３〜１；１、極めて特に
有利には１：３〜１：２の、式ＩＩＩｂ又は式ＩＩＩｃ
によるＮ−［Ｎ’−（２−アミノエチル）−２−アミノ
エチル］−３−アミノプロピルトリアルコキシシラン又
はアミノアルキルアルコキシシラン対式ＩＶによるフル
オルアルキルアルコキシシランの使用物質モル比によ
り、本発明による水溶性共縮合体中の特に高いフルオル
アルキル基含量を得ることができる。In particular, 1: ≦ 3.5, preferably 1: 3 to
1: 0.5, particularly preferably 1: 3-1; 1, very particularly preferably 1: 3-1: 2, of the formula IIIb or IIIc
According to the present invention, the molar ratio of N- [N '-(2-aminoethyl) -2-aminoethyl] -3-aminopropyl trialkoxysilane or aminoalkylalkoxysilane to fluoroalkylalkoxysilane according to formula IV , A particularly high fluoroalkyl group content in the water-soluble co-condensate can be obtained.

【００１４】本発明による組成物は任意の比で水で有利
に希釈することができる。その際、完全に加水分解され
た系では、通常付加的な加水分解アルコールが全く生じ
ない。通常本発明による組成物並びに希釈した系は、６
ヶ月以上にわたって非常に貯蔵安定性である。The composition according to the invention can be advantageously diluted with water in any ratio. In that case, a completely hydrolyzed system usually does not produce any additional hydrolyzed alcohol. Usually the composition according to the invention as well as the diluted system comprises 6
Very storage-stable for more than a month.

【００１５】従って、ヒドロキシ基−及び／又はアルコ
キシ基含有のオルガノシロキサン少なくとも１種及び水
を含有する組成物も本発明の目的であり、オルガノシロ
キサンが、 一般式Ｉ ［ＮＨx（ＣＨ2）aＮＨy（ＣＨ2）bＮＨz］− （Ｉ） ［その際、トリアミノ基は、Ｃ原子１〜４個を有するＮ
−結合アルキレン基少なくとも１個を介して珪素原子少
なくとも１個と結合しており、ａ及びｂは同一又は異な
るものであり、１〜６の整数を表わし、ｘは０又は１又
は２であり、ｙは０又は１であり、ｚは０又は１又は２
であり、（ｘ＋ｙ＋ｚ）≦４の条件を有する］のトリア
ミノ基少なくとも１個及び一般式ＩＩ Ｆ3Ｃ（ＣＦ2）r（ＣＨ2）s− （ＩＩ） ［式中、ｒは０〜１８の整数を表わし、ｓは０又は２で
ある］のＳｉ−Ｃ−結合フルオルアルキル基少なくとも
１個を有することを特徴とする。Accordingly, a composition comprising at least one hydroxy- and / or alkoxy-containing organosiloxane and water is also an object of the present invention, wherein the organosiloxane is of the general formula I [NH x (CH 2 ) a NH y (CH 2 ) b NH z ]-(I) [wherein the triamino group is an N having 1 to 4 C atoms
-Bonded to at least one silicon atom through at least one bonded alkylene group, a and b are the same or different and each represents an integer of 1 to 6, x is 0 or 1 or 2, y is 0 or 1 and z is 0 or 1 or 2
Wherein (x + y + z) ≦ 4 is satisfied] and at least one triamino group of the general formula II F 3 C (CF 2 ) r (CH 2 ) s − (II) wherein r is 0 to 18 Represents an integer, and s is 0 or 2.], wherein at least one Si-C-bonded fluoroalkyl group is provided.

【００１６】一般式Ｉ ［ＮＨx（ＣＨ2）aＮＨy（ＣＨ2）bＮＨz］− （Ｉ） ［その際、トリアミノ基は、Ｃ原子１〜４個を有するＮ
−結合アルキレン基少なくとも１個を介して珪素原子少
なくとも１個と結合しており、ａ及びｂは同一又は異な
るものであり、１〜６の整数を表わし、ｘは０又は１又
は２であり、ｙは０又は１であり、ｚは０又は１又は２
であり、（ｘ＋ｙ＋ｚ）≦４の条件を有する］のトリア
ミノ基少なくとも１個及び一般式ＩＩ Ｆ3Ｃ（ＣＦ2）r（ＣＨ2）s− （ＩＩ） ［式中、ｒは０〜１８の整数を表わし、ｓは０又は２で
ある］のＳｉ−Ｃ−結合フルオルアルキル基少なくとも
１個を含有する、オルガノシロキサンも本発明の目的で
ある。The general formula I [NH x (CH 2 ) a NH y (CH 2 ) b NH z ]-(I) wherein the triamino group is an N having 1 to 4 C atoms
-Bonded to at least one silicon atom through at least one bonded alkylene group, a and b are the same or different and each represents an integer of 1 to 6, x is 0 or 1 or 2, y is 0 or 1 and z is 0 or 1 or 2
Wherein (x + y + z) ≦ 4 is satisfied] and at least one triamino group of the general formula II F 3 C (CF 2 ) r (CH 2 ) s − (II) wherein r is 0 to 18 Represents an integer, s is 0 or 2], and is also an object of the present invention, which comprises at least one Si-C-bonded fluoroalkyl group.

【００１７】本発明によるオルガノシロキサンは通常、
当業者に公知であるような、いわゆる［Ｍ］−、［Ｄ］
−並びに［Ｔ］−構造単位をベースとし、その際、オリ
ゴマー又はポリマーのオルガノシロキサン単位は凝結体
を形成してもよい。The organosiloxane according to the invention is usually
So-called [M]-, [D] as known to those skilled in the art.
And [T] -structural units, where the oligomeric or polymeric organosiloxane units may form aggregates.

【００１８】このようなオルガノシロキサンは通常、本
発明のよる官能性基の他に、その他の官能基としてヒド
ロキシ基及び／又はアルコキシ基を有する。ヒドロキシ
−又はアルコキシ基の存在は通常製造で供給される水量
及びアルコール分離の完全性により調整することができ
る。更に本発明によるオルガノシロキサンは付加的な官
能基としてＣ原子１〜１６個を有するアルキル基を含
有、即ち有することができる。Such an organosiloxane usually has a hydroxy group and / or an alkoxy group as other functional groups in addition to the functional groups according to the present invention. The presence of hydroxy- or alkoxy groups can usually be adjusted by the amount of water supplied in the production and the completeness of the alcohol separation. Furthermore, the organosiloxanes according to the invention can contain, ie have, as additional functional groups, alkyl groups having 1 to 16 C atoms.

【００１９】特に本発明によるオルガノシロキサンは、
水で非常に良好に希釈することができる。その際、通常
低粘性の僅かに白濁した液体が得られる。しかし本発明
よるオルガノシロキサンはアルコール中にも溶解させる
ことができ又は水溶性乳濁液中に混入させることもでき
る。In particular, the organosiloxanes according to the invention are:
Very good dilution with water. At that time, a low-viscosity, slightly turbid liquid is usually obtained. However, the organosiloxanes according to the invention can also be dissolved in alcohols or can be incorporated into water-soluble emulsions.

【００２０】更にオルガノシロキサン含有組成物の製法
も本発明の目的であり、これは、 ｉ）一般式ＩＩＩａ ＮＨ2（ＣＨ2）2ＮＨ（ＣＨ2）2ＮＨ（ＣＨ2）3Ｓｉ
（Ｒ’）j（ＯＲ）(3-j)（ＩＩＩａ） ［式中、Ｒ及びＲ’は同一又は異なるものであり、Ｃ原
子１〜４個を有する線状又は枝分れアルキル基を表わ
し、ｊは０又は１である］及び／又は 一般式ＩＩＩｂ ［ＮＨ2（ＣＨ2）2］2Ｎ（ＣＨ2）3Ｓｉ（Ｒ’）k（Ｏ
Ｒ）(3-k) （ＩＩＩｂ） ［式中、Ｒ及びＲ’は同一又は異なるものであり、Ｃ原
子１〜４個を有する線状又は枝分れアルキル基を表わ
し、ｋは０又は１である］のアミノアルキルアルコキシ
シラン少なくとも１種及び／又は 一般式ＩＩＩｃ ［ＮＨx（ＣＨ2）aＮＨy（ＣＨ2）bＮＨz］・［（Ｃ
Ｈ2）cＳｉ（Ｒ′）d（ＯＲ）(3-d)］e （ＩＩＩｃ） ［式中、Ｒ及びＲ’は同一又は異なるものであり、Ｃ原
子１〜４個を有する線状又は枝分れアルキル基を表わ
し、ａは１〜６の整数を表わし、ｂは１、２、３、４、
５又は６であり、ｃは１、２、３又は４であり、ｄは０
又は１であり、ｅは１、２、３、４又は５であり、ｘは
０又は１又は２であり、ｙは０又は１であり、ｚは０又
は１又は２でありかつ（ｘ＋ｙ＋ｚ）≦４の条件を有
し、その際、ｅは（ｘ＋ｙ＋ｚ）＝０の場合には数値５
であり、（ｘ＋ｙ＋ｚ）＝１の場合にはｅ＝４であり、
（ｘ＋ｙ＋ｚ）＝２の場合にはｅ＝３であり、（ｘ＋ｙ
＋ｚ）＝３の場合にはｅ＝２であり、（ｘ＋ｙ＋ｚ）＝
４の場合にはｅ＝１である］の“ビスプロダクト”又は
“ビスプロダクト”の混合物 及びｉｉ）一般式ＩＶ Ｆ3Ｃ（ＣＦ2）r（ＣＨ2）sＳｉ（Ｒ”）t（ＯＲ）
(3-t) （ＩＶ） ［式中、ｒは０〜１８の整数であり、ｓは０又は２であ
り、ｔは０又は１であり、Ｒ及びＲ”は同一又は異なる
ものであり、Ｃ原子１〜４個を有する線状又は枝分れア
ルキル基を表わす］のフルオルアルキルアルコキシラン
少なくとも１種を混合し、水又は水／アルコール混合物
並びに場合により触媒を添加し、反応させ、アルコール
を完全にか又は部分的に除去することを特徴とする。こ
うして得た生成物混合物を無機又は有機酸の添加により
ｐＨ値＜１２に調整することが有利である。その際ｐＨ
値を４〜７に調整することが有利である。A further object of the present invention is a process for preparing the organosiloxane-containing composition, which comprises: i) the general formula IIIa: NH 2 (CH 2 ) 2 NH (CH 2 ) 2 NH (CH 2 ) 3 Si
(R ′) j (OR) (3-j) (IIIa) wherein R and R ′ are the same or different and represent a linear or branched alkyl group having 1 to 4 C atoms. , J is 0 or 1] and / or general formula IIIb [NH 2 (CH 2 ) 2 ] 2 N (CH 2 ) 3 Si (R ′) k (O
R) (3-k) (IIIb) wherein R and R ′ are the same or different and represent a linear or branched alkyl group having 1 to 4 C atoms, and k is 0 or 1 aminoalkyl alkoxysilanes at least one and / or the general formula IIIc of the is] [NH x (CH 2) a NH y (CH 2) b NH z] · [(C
H 2 ) c Si (R ′) d (OR) (3-d) ] e (IIIc) wherein R and R ′ are the same or different and are linear or having 1 to 4 C atoms or A represents an integer of 1 to 6, b represents 1, 2, 3, 4,
5 or 6, c is 1, 2, 3 or 4, and d is 0
Or 1, e is 1, 2, 3, 4 or 5, x is 0 or 1 or 2, y is 0 or 1, z is 0 or 1 or 2, and (x + y + z) ≦ 4, where e is the numerical value 5 if (x + y + z) = 0
And when (x + y + z) = 1, e = 4,
When (x + y + z) = 2, e = 3, and (x + y)
+ Z) = 3, e = 2, and (x + y + z) =
E = 1 in the case of 4) or a mixture of “bisproducts” and ii) the general formula IV F 3 C (CF 2 ) r (CH 2 ) s Si (R ″) t (OR )
(3-t) (IV) wherein r is an integer of 0 to 18, s is 0 or 2, t is 0 or 1, R and R ″ are the same or different, A linear or branched alkyl group having 1 to 4 carbon atoms], and reacting by adding water or a water / alcohol mixture and optionally a catalyst, The product mixture thus obtained is preferably adjusted to a pH of <12 by addition of an inorganic or organic acid.
It is advantageous to adjust the value to 4-7.

【００２１】更に、本発明の方法により得られる組成物
も本発明の目的である。本発明によるトリアミノ−及び
フルオルアルキル官能性オルガノシロキサン、特に本発
明の方法により得られるその混合物も本発明の目的であ
る。Furthermore, the composition obtained by the method of the present invention is also an object of the present invention. Triamino- and fluoroalkyl-functional organosiloxanes according to the invention, in particular the mixtures obtained by the process according to the invention, are also an object of the invention.

【００２２】本発明による方法で式ＩＩＩａによる成分
ｉ）としてＮ−［Ｎ’−（２−アミノエチル）−２−ア
ミノエチル］−３−アミノプロピルトリメトキシシラン
（ＤＹＮＡＳＹＬＡＮ(R)ＴＲＩＡＭＯ）を使用するの
が有利である。Using the - [(2-aminoethyl) -2-aminoethyl N ']-3-aminopropyltrimethoxysilane (DYNASYLAN (R) TRIAMO) [0022] as component i) according to formula IIIa in the process according to the invention N- Advantageously.

【００２３】式ＩＩＩｂによる成分の例として、 （Ｈ2Ｎ−ＣＨ2ＣＨ2）2Ｎ−（ＣＨ2）3Ｓｉ（ＯＣ
Ｈ3）3 が挙げられる。As an example of a component according to formula IIIb: (H 2 N—CH 2 CH 2 ) 2 N— (CH 2 ) 3 Si (OC
H 3 ) 3 .

【００２４】“ビスプロダクト”とは本発明では、一般
式ＩＩＩｃから想定されるような化合物、従って例え
ば、 （Ｈ3ＣＯ）3Ｓｉ（ＣＨ2）3ＮＨ（ＣＨ2）2ＮＨ（ＣＨ
2）2ＮＨ（ＣＨ2）3Ｓｉ（ＯＣＨ3）3 のようなものである。A "bisproduct" is defined in the present invention as a compound envisaged from the general formula IIIc, for example, (H 3 CO) 3 Si (CH 2 ) 3 NH (CH 2 ) 2 NH (CH
2 ) 2 NH (CH 2 ) 3 Si (OCH 3 ) 3 .

【００２５】しかし本発明による方法でトリアミノアル
キル−官能性アルコキシシランから成る混合物を使用す
ることもできる。However, it is also possible to use mixtures of triaminoalkyl-functional alkoxysilanes in the process according to the invention.

【００２６】一般式ＩＶのフルオルアルキルアルコキシ
シランとして本発明による方法では有利には、トリデカ
フルオル−１，１，２，２−テトラヒドロオクチルトリ
メトキシシラン又はトリデカフルオル−１，１，２，２
−テトラヒドロオクチルトリエトキシシラン（ＤＹＮＡ
ＳＹＬＡＮ(R)Ｆ８２６１）を使用する。しかし数種の
フルオルアルキルアルコキシシランの混合物を使用する
こともできる。The fluoroalkylalkoxysilanes of the general formula IV are preferably used in the process according to the invention in the form of tridecafluoro-1,1,2,2-tetrahydrooctyltrimethoxysilane or tridecafluoro-1,1,2,2.
-Tetrahydrooctyltriethoxysilane (DYNA
Using the SYLAN (R) F8261). However, it is also possible to use mixtures of several fluoroalkylalkoxysilanes.

【００２７】本発明による方法で使用するアルコキシシ
ランには、メトキシ−又はエトキシシランが挙げられ
る。方法の間にアルコールを添加する限り、相応するメ
タノール及び／又はエタノールを使用することができ
る。The alkoxysilanes used in the process according to the invention include methoxy- or ethoxysilane. As long as the alcohol is added during the process, the corresponding methanol and / or ethanol can be used.

【００２８】触媒として特にプロトン酸又はプロトン酸
から成る混合物が好適である。即ち、本発明による方法
では例えば蟻酸、酢酸並びに塩化水素を使用することが
できる。更に前記酸は本発明による組成物のｐＨ値の調
整用に使用することもできる。Protonic acids or mixtures comprising protonic acids are particularly suitable as catalysts. Thus, for example, formic acid, acetic acid and hydrogen chloride can be used in the process according to the invention. Furthermore, the acids can be used for adjusting the pH of the compositions according to the invention.

【００２９】本発明による方法で、ｉ）一般式ＩＩＩａ
からＩＩＩｃ）によるトリアミノシラン少なくとも１種
及びｉｉ）一般式ＩＶのフルオルアルキルシラン少なく
とも１種をｉ／ｉｉのモル比≧０．２９、有利には０．
３〜２、特に有利には０．３３〜０．５で使用する。In the process according to the invention, i) the general formula IIIa
To IIIc) and ii) at least one fluoroalkylsilane of the general formula IV with an i / ii molar ratio of ≧ 0.29, preferably 0.1%.
3 to 2, particularly preferably 0.33 to 0.5.

【００３０】更に本発明による水溶液中のオルガノシロ
キサン濃度を作用物質含量＜５０質量％に調整する。５
０質量％より上の作用物質含量によりゲル化又は強力な
混濁が生じる恐れがある。Furthermore, the concentration of the organosiloxane in the aqueous solution according to the invention is adjusted so that the active substance content is <50% by weight. 5
Gelling or strong turbidity may occur with active substance contents above 0% by weight.

【００３１】本発明による組成物中でオルガノシロキサ
ンの含量は、０．００５〜４０質量％、有利には０．０
１〜２０質量％、特に有利には０．０５〜１５質量％、
極めて特に有利には０．１〜５質量％である。The organosiloxane content in the composition according to the invention is from 0.005 to 40% by weight, preferably from 0.0
1 to 20% by weight, particularly preferably 0.05 to 15% by weight,
Very particularly preferably, 0.1 to 5% by weight.

【００３２】本発明による方法は通常、一般式ＩＩＩａ
からＩＩＩｃのアミノアルキルアルコキシシラン及び一
般式ＩＶのフルオルアルキルアルコキシシランを混合し
−場合によりアルコールを添加し−、一緒に加水分解
し、共縮合させ、加水分解アルコールも含めてアルコー
ルを蒸留により除去するようにして行う。アルコキシシ
ランの混合は、使用するシランの凝固点と沸点の間の温
度範囲で行うことができる。加水分解を実施するために
通常シラン混合物に過剰の水を添加する。その際、通常
ヒドロキシ官能性オルガノシロキサンが得られる。しか
し加水分解又は共縮合を化学量論的又は化学量論より下
の量の水を用いて行うこともできる。反応に供給する水
の量を使用するＳｉ−化合物１モル当たり水３モルより
少なく制限する限り、主としてアルコキシ含有の本発明
によるオルガノシロキサンを製造することができる。反
応で本発明によるオルガノシロキサンは通常は混合物と
して生じる。The process according to the invention generally has the general formula IIIa
To the aminoalkylalkoxysilanes of formula IIIc and the fluoroalkylalkoxysilanes of the general formula IV-optionally with the addition of alcohols-hydrolyzed together, co-condensed and the alcohol, including the hydrolyzed alcohol, is removed by distillation. Do so. The mixing of the alkoxysilane can be performed in a temperature range between the freezing point and the boiling point of the silane used. To carry out the hydrolysis, usually an excess of water is added to the silane mixture. In this case, a hydroxy-functional organosiloxane is usually obtained. However, the hydrolysis or co-condensation can also be carried out with stoichiometric or substoichiometric amounts of water. As long as the amount of water fed to the reaction is limited to less than 3 moles of water per mole of Si-compound, organosiloxanes according to the invention containing predominantly alkoxy can be prepared. In the reaction, the organosiloxane according to the invention is usually formed as a mixture.

【００３３】本発明による反応は通常は０〜１００℃の
範囲の温度で行う。本発明による反応をｐＨ値４〜１２
で行うのが好適である。加水分解を温度＜１００℃、特
に有利には＜９０℃、極めて特に有利には＜６０℃で行
うのが有利である。その際通常、例えば攪拌により良好
な混合が行われるように留意する。本明細書に記載の反
応は更に触媒の存在で行うことができる。The reaction according to the invention is usually carried out at a temperature in the range from 0 to 100 ° C. The reaction according to the invention is carried out at a pH of 4-12.
It is preferable to perform the above. The hydrolysis is preferably carried out at a temperature of <100 ° C., particularly preferably <90 ° C., very particularly preferably <60 ° C. At that time, care is usually taken to ensure good mixing, for example by stirring. The reactions described herein can be further performed in the presence of a catalyst.

【００３４】本発明による方法で通常アルコール又は加
水分解アルコールを蒸留により除去し、その際、蒸留を
有利には温度＜９０℃、特に有利には＜６０℃並びに好
適には−生成物保護作用があるので−減圧下で行う。そ
の際、組成物中のアルコール含量を下げて５質量％より
少なく、有利には１質量％より少なく、特に有利には
０．５質量％より少なくするのが好適である。In the process according to the invention, the alcohols or hydrolyzed alcohols are usually removed by distillation, whereby the distillation is preferably carried out at a temperature of <90 ° C., particularly preferably at <60 ° C. and preferably with a product protection action. Yes-under reduced pressure. It is preferred that the alcohol content in the composition is reduced to less than 5% by weight, preferably less than 1% by weight, particularly preferably less than 0.5% by weight.

【００３５】蒸留は有利には蒸留塔を用いて行い、塔の
頭頂部でもはやアルコールが確認されなくなるまで行う
ことができ、その際、たまり液中に所望の生成物が沈殿
し、場合により更に後処理することができる。混濁物質
が生じる場合には、これを濾過、沈降、遠心分離又は類
似の標準方法を用いて生成物から除去することができ
る。The distillation is advantageously carried out by means of a distillation column and can be carried out until no more alcohol is found at the top of the column, whereby the desired product precipitates in the pool and, if appropriate, It can be post-processed. If a turbid material forms, it can be removed from the product using filtration, sedimentation, centrifugation or similar standard methods.

【００３６】本発明による組成物の塗布は、５０％溶液
又は希釈した溶液から行うことができる。希釈剤として
例えば水を使用することができる。しかし基本的には本
発明による組成物を相応するアルコールで希釈してもよ
い。The application of the composition according to the invention can take place from a 50% solution or a diluted solution. For example, water can be used as a diluent. In principle, however, the compositions according to the invention may be diluted with the corresponding alcohols.

【００３７】本発明によるオルガノシロキサンを含有す
る薬剤、例えば−これだけに限定するものではないが−
表面の疎水化及び／又は疎油化、“アンチグラファイ
ト”加工、“イージー トゥ クリーン”加工（例をニ
三挙げたにすぎないが）用に使用されるようなものも本
発明の目的である。Agents containing the organosiloxanes according to the invention, such as, but not limited to,-
It is also an object of the present invention that it may be used for surface hydrophobization and / or oleophobization, "anti-graphite" processing, "easy to clean" processing (only a few examples). .

【００３８】従って本発明による組成物は、表面の疎水
化及び／又は疎油化用の薬剤として、建造物保護剤とし
て、コンクリート、鉱物性天然物並びに釉薬処理又は釉
薬未処理セラミック製品の処理用薬剤として、表面加工
用製剤中の添加物として、“アンチ−グラファイト”加
工用並びに“アンチ−グラファイト”加工用薬剤中へ、
“イージートゥクリーン”加工用並びに“イージートゥ
クリーン”加工用薬剤中へ、水溶性接着助剤として、塗
料系並びに腐蝕防止剤中の成分として、表面の殺生物加
工、木材の処理、皮革、皮革製品及び毛皮の処理、ガラ
ス表面処理、板ガラス処理、プラスチック表面処理、製
薬及び化粧品製造、ガラス−及び鉱物表面並びにガラス
−及び鉱物繊維表面の変性、人造石の製造、廃水処理、
顔料の表面変性及び処理用に並びに着色料及びラッカー
中の成分として、非常に有利に使用することができる。The compositions according to the invention can therefore be used as agents for hydrophobizing and / or oleophobizing surfaces, as building protection agents, for treating concrete, mineral natural products and glaze-treated or unglazed ceramic products. As a drug, as an additive in surface preparations, into "anti-graphite" processing and "anti-graphite" processing drugs,
In "Easy to Clean" processing and "Easy to Clean" processing chemicals, as a water-soluble adhesion aid, as a component in paint systems and corrosion inhibitors, surface biocidal processing, wood treatment, leather, leather Treatment of products and fur, glass surface treatment, sheet glass treatment, plastic surface treatment, pharmaceutical and cosmetics production, modification of glass and mineral surfaces and glass and mineral fiber surfaces, production of artificial stone, wastewater treatment,
It can be used very advantageously for the surface modification and treatment of pigments and as a component in colorants and lacquers.

【００３９】次に本発明を実施例に付き詳説する。Next, the present invention will be described in detail with reference to examples.

【００４０】[0040]

【実施例】 例１ モル比１：３のＤＹＮＡＳＹＬＡＮ(R)ＴＲＩＡＭＯ及びＤＹＮＡＳＹＬＡＮ( R) Ｆ８２６１からの水溶性縮合物の製造 装置 蒸留装置、内部温度計、添加装置を有する加熱可能な攪拌反応器 バランスシート 物質使用量 ｍ（ＤＹＮＡＳＹＬＡＮ(R)ＴＲＩＡＭＯ）＝ ２６．５ｇ ０．１モル ｍ（ＤＹＮＡＳＹＬＡＮ(R)Ｆ８２６１） ＝１５３．０ｇ ０．３モル ｍ（エタノール） ＝ ６０．０ｇ ｍ（水） ＝ １０．９ｇ １．５モル／Ｓｉモ ル （前加水分解） ｍ（蟻酸） ＝ １６．３ｇ ０．３モル （Ｂｉｅｓｔｅｒｆｅｌｄ、８５％ ） ｍ（水） ＝８６０．０ｇ 最終質量 ｍ（蒸留物） ＝ １１３．０ｇ ｍ（生成物） ＝１０２０．０ｇ 方法 ＴＲＩＡＭＯ２６．５ｇ及びＦ８２６１ １５３．０ｇ
及びエタノール６０ｇを前装入し、還流（約８０℃）で
２時間攪拌する。引き続き、約５０℃で前加水分解用の
水を添加する。反応混合物を８時間還流（約７８℃）で
加水分解する。その後、蟻酸（８５％）１６．３ｇを約
５０℃で添加し、水８６０ｇを添加する。その後生成物
は僅かに混濁している。EXAMPLES Example 1 molar ratio 1: Production apparatus distillation apparatus of the water-soluble condensation products from 3 of DYNASYLAN (R) TRIAMO and DYNASYLAN (R) F8261, internal thermometer, heatable stirred reactor balance with the addition device Sheet Material usage m (DYNASYLAN (R) TRIAMO) = 26.5 g 0.1 mol m (DYNASYLAN (R) F8261) = 153.0 g 0.3 mol m (ethanol) = 60.0 g m (water) = 10 9.9 g 1.5 mol / Si mol (pre-hydrolysis) m (formic acid) = 16.3 g 0.3 mol (Biestelfeld, 85%) m (water) = 860.0 g Final mass m (distillate) = 113 0.0 g m (product) = 1020.0 g Method TRIAMO 26.5 g and F8261 153.0 g
And 60 g of ethanol, and stirred at reflux (about 80 ° C.) for 2 hours. Subsequently, at about 50 ° C., water for prehydrolysis is added. The reaction mixture is hydrolyzed at reflux (about 78 ° C.) for 8 hours. Thereafter, 16.3 g of formic acid (85%) are added at about 50 ° C. and 860 g of water are added. Thereafter the product is slightly turbid.

【００４１】生じた加水分解アルコール及びエタノール
６０ｇを真空下で蒸留により除去する。The resulting hydrolyzed alcohol and 60 g of ethanol are removed by distillation under vacuum.

【００４２】圧力： １６０〜１３０ミリバール 内部温度：４８〜５０℃ ２９−Ｓｉ−ＮＭＲ−分析による生成物の試験から下記
が判明した：Ｓｉの１２．９モル％−モノマーのシラン
（トリアミノ官能性）及びＭ−構造（トリアミノ官能
性） Ｓｉの９．２モル％− Ｍ−構造（フルオルアルキル官
能性）及びＤ−構造（トリアミノ官能性）、 Ｓｉの６８．１モル％− Ｄ−構造（フルオルアルキル
官能性）及びＴ−構造（トリアミノ官能性）。Pressure: 160-130 mbar Internal temperature: 48-50 ° C. Examination of the product by 29-Si-NMR analysis revealed the following: 12.9 mol% of Si—monomer silane (triamino functionality) And M-structure (triamino-functional) 9.2 mol% of Si-M-structure (fluoroalkyl-functional) and D-structure (triamino-functional), 68.1 mol% of Si-D-structure (full Orthoalkyl functionality) and T-structure (triamino functionality).

【００４３】更に、０．０３７４μｍの平均粒度Ｄ50
（レーザー光線）が判明した。Furthermore, an average particle size D50 of 0.0374 μm
(Laser beam) turned out.

【００４４】例２ 例１からの生成物を水で希釈して最初に使用したフルオ
ルアルキルトリアルコキシシランの濃度ａ）１％、ｂ）
０．１％、ｃ）０．０５％にする。Example 2 The concentration of the fluoroalkyl trialkoxysilane initially used after diluting the product from Example 1 with water a) 1%, b)
0.1%, c) 0.05%.

【００４５】比較用に欧州特許第０８４６７１６Ａ２号
明細書に記載の共縮合物をアミノプロピルトリエトキシ
シラン及びＤＹＮＡＳＹＬＡＮ(R)Ｆ８２６１から製造
し（欧州特許第０８４６７１６Ａ２号明細書の例２参
照）、水で同じフルオルシラン含量に希釈する：溶液
ｄ）、ｅ）、ｆ）。[0045] The co-condensation product according to EP 0846716A2 for comparison was prepared from aminopropyltriethoxysilane and DYNASYLAN (R) F8261 (see Example 2 of EP 0846716A2), with water Dilute to the same fluorosilane content: solutions d), e), f).

【００４６】多孔性鉱物支持体への試験前記溶液中に、
１辺の長さ約１０ｃｍの石灰砂岩試験体を各々１０秒間
浸す。約１時間空気中で乾燥後、試験体を水及び鉱物油
（Ｋａｙｄｏｌ、ＣＡＳ８０１２−９５−１）に関して
撥液体特性を比較試験する。Testing on a porous mineral support
A lime-sandstone specimen having a side length of about 10 cm is immersed for 10 seconds each. After drying in air for about 1 hour, the test specimens are compared for liquid repellency properties with water and mineral oil (Kaydol, CAS8012-95-1).

【００４７】水に関する撥液体試験は全ての場合（ａか
らｆ）に優れている。ロールオフ角（＝特定の大きさの
水１滴を転がすために必要な傾斜−視覚試験：ロールオ
フ角が小さければ小さい程、撥液体性は良好である）
は、勿論ａ）、ｂ）及びｃ）で相応する比較溶液ｄ）、
ｅ）及びｆ）より著しく僅か（従って良好）である。特
に疎油性の観察で相違が著しい。試験体表面上に塗布し
た鉱物油（Ｋａｙｄｏｌ）の水滴はａ）及びｂ）では３
０秒間の作用時間後に全く斑点を生じず、ｃ）では僅か
な斑点形成が観察される（これは油の多孔性鉱物試験体
への浸透開始を表わすものである）。ｄ）の場合には同
じ操作方法で僅かな斑点形成が認められ、ｅ）及びｆ）
の場合には強力な斑点形成又は油滴の完全な吸収が認め
られる。The liquid repellency test for water is excellent in all cases (a to f). Roll-off angle (= tilt required to roll one drop of water of specific size-visual test: the smaller the roll-off angle, the better the liquid repellency)
Are, of course, the corresponding comparative solutions d), a), b) and c)
significantly less (and thus better) than e) and f). In particular, the difference is remarkable in the observation of oleophobicity. Water droplets of mineral oil (Kaydol) applied on the surface of the test specimen were 3 in a) and b).
No spotting occurs after an action time of 0 s and a slight spotting is observed in c) (indicating the onset of penetration of the oil into the porous mineral specimen). In the case of d), slight spot formation was observed by the same operation method, and e) and f)
In the case of strong spotting or complete absorption of the oil droplets is observed.

【００４８】結果：本発明による組成物は、公知技術に
よる比較可能な生成物に比して、多孔性鉱物支持体上に
より良好な疎水及び疎油性特性を付与する。Result: The composition according to the invention gives better hydrophobic and oleophobic properties on a porous mineral support compared to comparable products according to the prior art.

【００４９】ガラス上での試験 ガラス製スライドガラス（約７６×２６ｍｍ、直ちに使
用できるようにきれいにした、Ｍｅｎｚｅｌ−Ｇｌａｅ
ｓｅｒ、商品番号０１１１０１）を各々１分間溶液ａ）
又はｄ）中に浸す。乾燥後、水に対する静的接触角をＤ
ＩＮ ＥＮ ８２８により測定する。Tests on glass Glass slides (approximately 76 × 26 mm, Menzel-Glae cleaned for immediate use)
Ser, product number 011101) for 1 minute each in solution a)
Or d. After drying, the static contact angle against water is D
Measured according to IN EN 828.

【００５０】溶液ａ）で処理したガラス板は接触角１０
４°を示し、溶液ｄ）で処理したガラス板は接触角８７
°しか示さない。未処理ガラス板は接触角＜３０°を示
す。The glass plate treated with solution a) has a contact angle of 10
The glass plate showing 4 ° and treated with solution d) had a contact angle of 87
Only show °. The untreated glass plate shows a contact angle <30 °.

【００５１】従って本発明による例１からの生成物は、
公知技術による比較可能な生成物に対して平滑な表面
（ガラス）に対してもより良好な撥液体特性を有する。Thus, the product from Example 1 according to the invention is:
It also has better liquid-repellent properties on smooth surfaces (glass) for comparable products according to the prior art.

【００５２】 例３ モル比１：２：１のＤＹＮＡＳＹＬＡＮ(R)ＴＲＩＡＭＯ、ＤＹＮＡＳＹＬＡ Ｎ(R)Ｆ８２６１及びヘキサデシルトリメトキシシラン（ＤＹＮＡＳＹＬＡＮ(R) ９１１６）からの水溶性縮合物の製造 装置 蒸留装置、内部温度計、添加装置を有する加熱可能な攪拌反応器 バランスシート 物質使用量 ｍ（ＤＹＮＡＳＹＬＡＮ(R)ＴＲＩＡＭＯ）＝ ５．３ｇ ０．０２モル ｍ（ＤＹＮＡＳＹＬＡＮ(R)Ｆ８２６１） ＝ ２０．４ｇ ０．０４モル ｍ（ＤＹＮＡＳＹＬＡＮ(R)９１１６） ＝ ３．５ｇ ０．０２モル ｍ（エタノール） ＝ １２．０ｇ ｍ（水） ＝ ２．１６ｇ ｍ（蟻酸） ＝ ３．２ｇ （Ｂｉｅｓｔｅｒｆｅｌｄ、８５％ ） ｍ（水） ＝１７０．０ｇ 最終質量 ｍ（蒸留物） ＝ ９７．９ｇ ｍ（生成物） ＝１１８．５ｇ 方法 ＴＲＩＡＭＯ、Ｆ８２６１及びエタノールを前装入し、
還流（約８０℃）で２時間攪拌する。引き続き、約５０
℃で前加水分解用の水を添加する。反応混合物を８時間
還流（約７８℃）で加水分解する。その後蟻酸（８５
％）を約５０℃で添加し、残りの水を添加する。その後
生成物は僅かに混濁している。[0052] Example 3 molar ratio of 1: 2: 1 of DYNASYLAN (R) TRIAMO, manufacturing apparatus distillation apparatus of a water-soluble condensate from DYNASYLA N (R) F8261 and hexadecyl trimethoxysilane (DYNASYLAN (R) 9116), internal thermometer, heatable stirred reactor balance sheet material usage m having a dosing device (DYNASYLAN (R) TRIAMO) = 5.3g 0.02 mol m (DYNASYLAN (R) F8261) = 20.4g 0.04 Mol m (DYNASYLAN (R) 9116) = 3.5 g 0.02 mol m (ethanol) = 12.0 g m (water) = 2.16 g m (formic acid) = 3.2 g (Biesfeldeld, 85%) m (water) ) = 170.0 g Final mass m (distillate) = 97.9 g m (product) = 118.5 g The law TRIAMO, F8261 and ethanol MaeSoIri,
Stir at reflux (about 80 ° C.) for 2 hours. About 50
Add water for prehydrolysis at 0 ° C. The reaction mixture is hydrolyzed at reflux (about 78 ° C.) for 8 hours. Then, formic acid (85
%) At about 50 ° C. and the remaining water is added. Thereafter the product is slightly turbid.

【００５３】生じた加水分解アルコール及び付加的に添
加したエタノールを真空下で蒸留により除去する。The resulting hydrolyzed alcohol and additionally added ethanol are removed by distillation under vacuum.

【００５４】圧力： １６０〜１３０ミリバール 内部温度：４８〜５０℃ 得られた生成物は、僅かに混濁しており、任意の比で水
と混合可能である。Pressure: 160-130 mbar Internal temperature: 48-50 ° C. The product obtained is slightly turbid and can be mixed with water in any ratio.

【００５５】生成物６．６７ｇに水９３．３３ｇを加
え、石灰砂岩表面に塗布する。乾燥後、優れた水に対す
る撥液体特性が観察される。To 6.67 g of the product, 93.33 g of water is added and applied to the surface of lime-sandstone. After drying, excellent liquid repellent properties to water are observed.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 ブルクハルト シュタントケ ドイツ連邦共和国 レルラッハ クリショ ナシュトラーセ 25 (72)発明者 ヤラスロフ モンキーヴィッツ ドイツ連邦共和国 ラインフェルデン ブ ルステルシュトラーセ ２ アー (72)発明者 ミヒャエル ホルン ドイツ連邦共和国 ラインフェルデン マ イゼンライン 11 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Burghard Standke Germany Lerlach Crischo Nastrasse 25 (72) Inventor Yaraslov Monkeywitz Germany Rheinfelden Bürsterstrasse 2 aar (72) Inventor Michael Horn Germany Republic of Rheinfelden-Maisenlein 11

Claims (20)

【特許請求の範囲】[Claims] 【請求項１】 一般式Ｉ ［ＮＨx（ＣＨ2）aＮＨy（ＣＨ2）bＮＨz］− （Ｉ） ［その際、これは、Ｃ原子１〜４個を有するＮ−結合ア
ルキレン基少なくとも１個を介して珪素原子少なくとも
１個と結合しており、ａ及びｂは同一又は異なるもので
あり、１〜６の整数を表わし、ｘは０又は１又は２であ
り、ｙは０又は１であり、ｚは０又は１又は２であり、
（ｘ＋ｙ＋ｚ）≦４の条件を有する］のトリアミノ基少
なくとも１個及び一般式ＩＩ Ｆ3Ｃ（ＣＦ2）r（ＣＨ2）s− （ＩＩ） ［式中、ｒは０〜１８の整数を表わし、ｓは０又は２で
ある］のＳｉ−Ｃ−結合フルオルアルキル基少なくとも
１個を特徴とする、オルガノシロキサン。1. A compound of the general formula I [NH x (CH 2 ) a NH y (CH 2 ) b NH z ]-(I) wherein an N-linked alkylene group having 1 to 4 C atoms Bonded to at least one silicon atom via at least one atom, a and b are the same or different and each represents an integer of 1 to 6, x is 0 or 1 or 2, y is 0 or 1, z is 0 or 1 or 2,
(X + y + z) ≦ 4] and at least one triamino group of the general formula II F 3 C (CF 2 ) r (CH 2 ) s − (II) wherein r represents an integer of 0 to 18 , S is 0 or 2], wherein at least one Si-C-bonded fluoroalkyl group is used. 【請求項２】 オルガノシロキサンが、一般式Ｉ ［ＮＨx（ＣＨ2）aＮＨy（ＣＨ2）bＮＨz］− （Ｉ） ［その際、これは、Ｃ原子１〜４個を有するＮ−結合ア
ルキレン基少なくとも１個を介して珪素原子少なくとも
１個と結合しており、ａ及びｂは同一又は異なるもので
あり、１〜６の整数を表わし、ｘは０又は１又は２であ
り、ｙは０又は１であり、ｚは０又は１又は２であり、
（ｘ＋ｙ＋ｚ）≦４の条件を有する］のトリアミノ基少
なくとも１個及び一般式ＩＩ Ｆ3Ｃ（ＣＦ2）r（ＣＨ2）s− （ＩＩ） ［式中、ｒは０〜１８の整数を表わし、ｓは０又は２で
ある］のＳｉ−Ｃ−結合フルオルアルキル基少なくとも
１個を有することを特徴とする、ヒドロキシ基及び／又
はアルコキシ基含有オルガノシロキサン少なくとも１種
及び水を含有する組成物。2. An organosiloxane having the general formula I [NH x (CH 2 ) a NH y (CH 2 ) b NH z ]-(I) where -Bonded to at least one silicon atom through at least one bonded alkylene group, a and b are the same or different and each represents an integer of 1 to 6, x is 0 or 1 or 2, y is 0 or 1, z is 0 or 1 or 2,
(X + y + z) ≦ 4] and at least one triamino group of the general formula II F 3 C (CF 2 ) r (CH 2 ) s − (II) wherein r represents an integer of 0 to 18 , S is 0 or 2.] A composition comprising at least one hydroxy- and / or alkoxy-containing organosiloxane and water, characterized in that it has at least one Si-C-bonded fluoroalkyl group. . 【請求項３】 オルガノシロキサン及び／又はオルガノ
シロキサン混合物中の式Ｉ及びＩＩによる基のモル比が
１：≦３．５であることを特徴とする、請求項２に記載
の組成物。3. The composition according to claim 2, wherein the molar ratio of the groups according to formulas I and II in the organosiloxane and / or the organosiloxane mixture is 1: ≦ 3.5. 【請求項４】 オルガノシロキサンの含量が組成物に対
して０．００５〜４０質量％であることを特徴とする、
請求項２又は３に記載の組成物。4. The composition according to claim 1, wherein the content of the organosiloxane is 0.005 to 40% by mass based on the composition.
The composition according to claim 2. 【請求項５】 １１より少ないｐＨ値を特徴とする、請
求項２から４までのいずれか１項に記載の組成物。5. The composition according to claim 2, wherein the composition has a pH of less than 11. 【請求項６】 ５質量％より少ないアルコール含量を特
徴とする、請求項２から５までのいずれか１項に記載の
組成物。6. The composition according to claim 2, wherein the composition has an alcohol content of less than 5% by weight. 【請求項７】 請求項１から６までのいずれか１項に記
載のオルガノシロキサン含有組成物を製造するに当た
り、 ｉ）一般式ＩＩＩａ ＮＨ2（ＣＨ2）2ＮＨ（ＣＨ2）2ＮＨ（ＣＨ2）3Ｓｉ
（Ｒ’）j（ＯＲ）(3-j)（ＩＩＩａ） ［式中、Ｒ及びＲ’は同一又は異なるものであり、Ｃ原
子１〜４個を有する線状又は枝分れアルキル基を表わ
し、ｊは０又は１である］及び／又は 一般式ＩＩＩｂ ［ＮＨ2（ＣＨ2）2］2Ｎ（ＣＨ2）3Ｓｉ（Ｒ’）k（Ｏ
Ｒ）(3-k) （ＩＩＩｂ） ［式中、Ｒ及びＲ’は同一又は異なるものであり、Ｃ原
子１〜４個を有する線状又は枝分れアルキル基を表わ
し、ｋは０又は１である］のアミノアルキルアルコキシ
シラン少なくとも１種及び／又は 一般式ＩＩＩｃ ［ＮＨx（ＣＨ2）aＮＨy（ＣＨ2）bＮＨz］・［（Ｃ
Ｈ2）cＳｉ（Ｒ’）d（ＯＲ）(3-d)］e （ＩＩＩｃ） ［式中、Ｒ及びＲ’は同一又は異なるものであり、Ｃ原
子１〜４個を有する線状又は枝分れアルキル基を表わ
し、ａは１〜６の整数を表わし、ｂは１、２、３、４、
５又は６であり、ｃは１、２、３又は４であり、ｄは０
又は１であり、ｅは１、２、３、４又は５であり、ｘは
０又は１又は２であり、ｙは０又は１であり、ｚは０又
は１又は２でありかつ（ｘ＋ｙ＋ｚ）≦４の条件を有
し、その際、ｅは（ｘ＋ｙ＋ｚ）＝０の場合には数値５
であり、（ｘ＋ｙ＋ｚ）＝１の場合にはｅ＝４であり、
（ｘ＋ｙ＋ｚ）＝２の場合にはｅ＝３であり、（ｘ＋ｙ
＋ｚ）＝３の場合にはｅ＝２であり、（ｘ＋ｙ＋ｚ）＝
４の場合にはｅ＝１である］の“ビスプロダクト”又は
“ビスプロダクト”の混合物及び ｉｉ）一般式ＩＶ Ｆ3Ｃ（ＣＦ2）r（ＣＨ2）sＳｉ（Ｒ”）t（ＯＲ）
(3-t) （ＩＶ） ［式中、ｒは０〜１８の整数であり、ｓは０又は２であ
り、ｔは０又は１であり、Ｒ及びＲ”は同一又は異なる
ものであり、Ｃ原子１〜４個を有する線状又は枝分れア
ルキル基を表わす］のフルオルアルキルアルコキシラン
少なくとも１種を混合し、水又は水／アルコール混合物
を添加し、反応させ、アルコールを完全にか又は部分的
に除去することを特徴とする、請求項１から６までのい
ずれか１項に記載のオルガノシロキサン含有組成物の製
法。7. The method for producing an organosiloxane-containing composition according to claim 1, comprising the steps of: i) the general formula IIIa NH 2 (CH 2 ) 2 NH (CH 2 ) 2 NH (CH) 2) 3 Si
(R ′) j (OR) (3-j) (IIIa) wherein R and R ′ are the same or different and represent a linear or branched alkyl group having 1 to 4 C atoms. , J is 0 or 1] and / or general formula IIIb [NH 2 (CH 2 ) 2 ] 2 N (CH 2 ) 3 Si (R ′) k (O
R) (3-k) (IIIb) wherein R and R ′ are the same or different and represent a linear or branched alkyl group having 1 to 4 C atoms, and k is 0 or 1 aminoalkyl alkoxysilanes at least one and / or the general formula IIIc of the is] [NH x (CH 2) a NH y (CH 2) b NH z] · [(C
H 2 ) c Si (R ′) d (OR) (3-d) ] e (IIIc) wherein R and R ′ are the same or different and are linear or having 1 to 4 C atoms or A represents an integer of 1 to 6, b represents 1, 2, 3, 4,
5 or 6, c is 1, 2, 3 or 4, and d is 0
Or 1, e is 1, 2, 3, 4 or 5, x is 0 or 1 or 2, y is 0 or 1, z is 0 or 1 or 2, and (x + y + z) ≦ 4, where e is the numerical value 5 if (x + y + z) = 0
And when (x + y + z) = 1, e = 4,
When (x + y + z) = 2, e = 3, and (x + y)
+ Z) = 3, e = 2, and (x + y + z) =
E = 1 in the case of 4) or a mixture of “bisproducts” and ii) the general formula IV F 3 C (CF 2 ) r (CH 2 ) s Si (R ″) t (OR )
(3-t) (IV) wherein r is an integer of 0 to 18, s is 0 or 2, t is 0 or 1, R and R ″ are the same or different, Represents a linear or branched alkyl group having 1 to 4 carbon atoms], and adding water or a water / alcohol mixture and reacting to completely remove the alcohol. The method for producing an organosiloxane-containing composition according to any one of claims 1 to 6, wherein the composition is partially removed. 【請求項８】 ｉ）一般式ＩＩＩａからＩＩＩｃによる
トリアミノシラン少なくとも１種及びｉｉ）一般式ＩＶ
のフルオルアルキルシラン少なくとも１種をモル比ｉ／
ｉｉ≧０．２９で使用することを特徴とする、請求項７
に記載の製法。8. A compound of the general formula IIIa to IIIc and at least one triaminosilane and ii) a general formula IV
At least one of the fluoroalkylsilanes having a molar ratio of i /
8. The method according to claim 7, wherein ii ≧ 0.29.
Production method described in 1. 【請求項９】 成分ｉ）及びｉｉ）の他にＣ1〜Ｃ16−
アルキルアルコキシシランを使用することを特徴とす
る、請求項７又は８に記載の製法。9. In addition to components i) and ii), C1 -C16-
The method according to claim 7, wherein an alkylalkoxysilane is used. 【請求項１０】 アルコキシシランから成る混合物に反
応前にアルコールを添加することを特徴とする、請求項
７から９までのいずれか１項に記載の製法。10. The process according to claim 7, wherein an alcohol is added to the mixture comprising the alkoxysilane before the reaction. 【請求項１１】 反応を温度＜１００℃で行うことを特
徴とする、請求項７から１０までのいずれか１項に記載
の製法。11. The process according to claim 7, wherein the reaction is carried out at a temperature of <100 ° C. 【請求項１２】 反応を触媒としてプロトン酸の存在で
行うことを特徴とする、請求項７から１１までのいずれ
か１項に記載の製法。12. The process according to claim 7, wherein the reaction is carried out in the presence of a protonic acid as a catalyst. 【請求項１３】 反応をｐＨ値４〜１２で行うことを特
徴とする、請求項７から１２までのいずれか１項に記載
の製法。13. The process according to claim 7, wherein the reaction is carried out at a pH of 4 to 12. 【請求項１４】 反応により得られた生成物混合物から
アルコールを５質量％より少ない含量まで除去すること
を特徴とする、請求項７から１３までのいずれか１項に
記載の製法。14. The process according to claim 7, wherein the alcohol is removed from the product mixture obtained by the reaction to a content of less than 5% by weight. 【請求項１５】 生成物混合物をアルコールの除去後に
無機又は有機酸の添加によりｐＨ値＜１２にすることを
特徴とする、請求項７から１４までのいずれか１項に記
載の製法。15. The process according to claim 7, wherein the pH of the product mixture is adjusted to <12 by adding an inorganic or organic acid after removing the alcohol. 【請求項１６】 触媒として及び／又はｐＨ値調整用の
酸として塩化水素、酢酸又は蟻酸を使用することを特徴
とする、請求項７から１５までのいずれか１項に記載の
製法。16. The process according to claim 7, wherein hydrogen chloride, acetic acid or formic acid is used as a catalyst and / or as an acid for adjusting the pH value. 【請求項１７】 請求項７から１６までのいずれか１項
により得られる組成物。17. A composition obtained according to any one of claims 7 to 16. 【請求項１８】 請求項７から１６までのいずれか１項
により得られる、トリアミノ−及びフルオルアルキル官
能性オルガノシロキサン並びにその混合物。18. Triamino- and fluoroalkyl-functional organosiloxanes obtained according to any one of claims 7 to 16 and mixtures thereof. 【請求項１９】 請求項１から１８までのいずれか１項
によるオルガノシロキサンを含有する薬剤。19. A medicament comprising an organosiloxane according to any one of claims 1 to 18. 【請求項２０】 請求項１から１９までのいずれか１項
によるトリアミノ−及びフルオルアルキル官能性オルガ
ノシロキサンの、表面の疎水化及び／又は疎油化用の薬
剤として並びに薬剤中へ、建造物保護剤として、コンク
リート、鉱物性天然物並びに釉薬処理又は釉薬未処理セ
ラミック製品の処理用薬剤として並びに薬剤中へ、表面
加工用製剤中の添加物として、“アンチ−グラファイト
（Ａｎｔｉ−Ｇｒａｆｆｉｔｉ）”加工用並びに“アン
チ−グラファイト”加工用薬剤中へ、“イージートゥク
リーン（Ｅａｓｙ ｔｏ ｃｌｅａｎ）”加工用の並び
に“イージートゥクリーン”加工用薬剤中へ、水溶性接
着助剤として、塗料系並びに腐蝕防止剤中の成分とし
て、表面の殺生物加工用、木材の処理用、皮革、皮革製
品及び毛皮の処理用、ガラス表面処理用、板ガラス処理
用、プラスチック表面処理用、製薬及び化粧品製造用、
ガラス−及び鉱物表面並びにガラス−及び鉱物繊維表面
の変性用、人造石の製造用、廃水処理用、顔料の表面変
性及び処理用並びに着色料及びラッカー中の成分として
の使用。20. Structures of the triamino- and fluoroalkyl-functional organosiloxanes according to claim 1 as surface-hydrophobic and / or oleophobic agents and in the drug. As a protective agent, as an agent for the treatment of concrete, mineral natural products and glaze-treated or unglazed ceramic products, as well as into the agent, as an additive in surface preparations, "anti-graphite" processing As a water-soluble adhesive aid in paints and anti-graphite processing agents, in "Easy to clean" processing agents and in "Easy to clean" processing agents, paint systems and corrosion protection Ingredients include biocidal processing of surface, wood treatment, leather, leather products and fur treatment, Scan the surface for processing, for flat glass processing, plastic surface treatment, pharmaceutical and cosmetic production,
Use for modifying glass and mineral surfaces and glass and mineral fiber surfaces, for producing artificial stones, for treating wastewater, for modifying and treating pigment surfaces and as a component in colorants and lacquers.
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